Composite article

ABSTRACT

A fiber-reinforced composite article useful for contaminant removal comprising at least one single layer of a fiber-reinforced composite having (a) at least one first polymer fiber-free region containing material adapted for removing contaminants, (b) at least one second polymer fiber-rich region containing fiber reinforcement material; and (c) at least one third polymer boundary region containing a portion of the first polymer fiber-free region and a portion of the second polymer fiber-rich region; a process for manufacturing the fiber-reinforced composite article; and a process for removing contaminants from a liquid fluid using the fiber-reinforced composite article.

FIELD

The present invention is related to a composite article useful forremoving contaminants from a liquid fluid; and to a process formanufacturing the composite article.

INTRODUCTION

Heretofore, various pipe structures and methods have been used forremoving contaminants from liquid fluids flowing through the interiorspace of the pipe structures. Typically, the known methods for removingcontaminants are based on coatings applied to metal pipe substrates(e.g., steel, aluminum, and the like). For example,

U.S. Pat. Nos. 8,726,989 and 8,746,335 disclose methods for removingcontaminants from wastewater during a hydraulic fracturing processutilizing a pipe coating on the inner surface of a pipe to capturecontaminants from the hydraulic fracturing operation. The use of acoating applied to the inner surface of a pipe to capture contaminantshas its disadvantages including, among others, the followingdisadvantages: (1) an extra layer is required for the overall structureof the pipe; (2) the added extra coating layer reduces the innerdiameter of the pipe, thus constricting the space that fluid can flowinside the pipe; and (3) an additional processing step is required forapplying the coating layer to the pipe when the pipe is beingmanufacturing. Furthermore, the processes of the above patents do notprovide for a contaminant removal mechanism which is incorporateddirectly into a pipe structure, that is, the pipe structure does notinclude an integral contaminant removal layer bonded to the pipestructure.

U.S. Pat. No. 4,171,238 discloses a method of making reinforced plasticcomposite structures. The above patent describes the incorporation ofmicron-size particulate, such as cement particles, for the purpose ofreducing the amount of wear that occurs inside of a pipe, that is, theabove patent is concerned with increasing resistance to acids or othercorrosive materials. The patent further discloses an attempt to make aparticulate and resin bonded together in a single matrix wherein theparticulate is suspended inside the resin such as a polyester resin. Theabove known process disclosed in U.S. Pat. No. 4,171,238 suffers fromthe disadvantage of requiring the distribution of particles throughoutall fiber reinforced regions and the inability to preferentially place apredetermined amount of particles in a predetermined fiber reinforcedregion of the fiber reinforced composite to maximize functionalizationwhile minimizing cost.

In U.S. Pat. No. 6,620,475, a structure for a wound fiber reinforcedplastic tubing and method for making the tubing is described. The abovepatent describes the formation and manufacture of a fiber-reinforcedcomposite pipe through a filament winding process using an inner linerand one or more layers of fiber reinforcing material. The above knownprocess disclosed in U.S. Pat. No. 6,620,475 does not utilize the innerliner of the composite material as a multifunctional material that isable to capture unwanted contaminants from a flowing fluid coming indirect contact with the surface of the inner liner.

SUMMARY

Embodiments may be realized by providing a fiber-reinforced compositearticle useful for contaminant removal. The fiber-reinforced compositeincludes at least one single layer of a fiber-reinforced compositecomprising several sections, areas or regions making up the single layerof the composite. For example, the composite may include the followingregions in the at least one single layer: (a) at least one first polymerfiber-free region containing material adapted for removing contaminants,said contaminant removal material integrated into the first polymerfiber-free region; said first polymer fiber-free region including aninner surface and an outer surface; (b) at least one second polymerfiber-rich region containing fiber reinforcement material; said secondpolymer fiber-rich region including an inner surface and an outersurface; and (c) at least one third polymer boundary region containing aportion of the first polymer fiber-free region and a portion of thesecond polymer fiber-rich region; wherein the outer surface of the firstpolymer fiber-free region is integrally bonded to the inner surface ofthe second polymer fiber-rich region forming the at least one thirdpolymer boundary region disposed between the first polymer fiber-freeregion and the second polymer fiber-rich region; wherein the thirdpolymer boundary region further comprises a contiguous boundary of anon-delineated width between the first polymer fiber-free region and thesecond polymer fiber-rich region; and wherein the first polymerfiber-free region is integrally attached to the second polymerfiber-rich region such that the first polymer fiber-free region andsecond polymer fiber-rich region are infused together forming the atleast one third polymer boundary region.

Another embodiment of the present invention is directed to a process formaking the above composite article. Other embodiments of the presentinvention include an apparatus and process of manufacturing afiber-reinforced composite article. Still another embodiment of thepresent invention is directed to a process for removing contaminantsusing the above composite article, particularly when the compositearticle is a conduit such as a pipe.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purpose of illustrating the present invention, the drawings showa form of the present invention which is presently preferred. However,it should be understood that the present invention is not limited to theprecise arrangements and instrumentation shown in the drawings. In thedrawings, like elements are referenced with like numerals. Therefore,the following drawings illustrate non-limiting embodiments of thepresent invention wherein:

FIG. 1 is a schematic cross-sectional view of one embodiment of thecomposite article structure, shown as a pipe member, including thematerials used to form the layers of a composite structure of thepresent invention. FIG. 1 includes a first polymer fiber-free regioncontaining material adapted for removing contaminants, a second polymerfiber-rich region containing fiber reinforcement material, and a thirdpolymer boundary region disposed in between the first polymer fiber-freeregion and the second polymer fiber-rich region wherein the thirdpolymer boundary region contains a portion of the first polymerfiber-free region and a portion of the second polymer fiber-rich regionintegrally bonded together.

FIG. 2 is a micrograph (at 5× magnification) of a portion of a pipemember structure of the present invention showing a homogenous bondingregion (as shown between dotted lines A and B) between the first polymerfiber-free region (as shown between dotted lines B and C) and the secondpolymer fiber-rich region (as shown as numeral 22).

FIG. 3 is a micrograph (at 10× magnification) of a portion of a pipemember structure of the present invention showing a homogenous bondingregion (as shown between dotted lines D and E) between the first polymerfiber-free region (as shown between dotted lines E and F) and the secondpolymer fiber-rich region (as shown as numeral 32).

FIG. 4 is a schematic cross-sectional view of another embodiment of thecomposite article structure, shown as a multi-layer pipe member,including the materials used to form various layers of a compositestructure of the present invention. While FIG. 4 shows at least fivelayers comprising the layered pipe member structure, the presentinvention composite article is not limited to a specific number oflayers because the minimum number of layers required for a particularapplication can vary by application and operating conditions of thefabricated composite pipe. The minimum number of layers in the pipe ofthe present invention may be as little as one layer comprising thedifferent regions in the cross-sectional view shown in FIG. 1.

FIG. 5 is a photograph showing the application of a first polymerfiber-free gel layer to a mandrel of a filament winding apparatus duringthe manufacturing process of the pipe structure of the presentinvention.

FIG. 6 is a photograph showing the application of a wound second polymerfiber-rich composite over the first polymer fiber-free gel layer of FIG.5 during the manufacturing process of the pipe structure of the presentinvention.

DETAILED DESCRIPTION

The present invention solves several problems of the known processes.For example, the process of the present invention provides a contaminantremoval mechanism which is incorporated directly into an article, suchas a pipe, reducing the time required to fabricate a composite structureor part. In addition, the composite fabrication process allows for theproduction of an article of varying sizes such as a pipe with innerdiameters of less than one inch. Furthermore, the present inventiondemonstrates that functional additives can be preferentially placed in afiber reinforced composite to maximize functionalization whileminimizing cost. And, the composite structure of the present inventionutilizes one or more of the composite's structural parts, such as theinner liner of a composite pipe material, as a multifunctional materialthat is able to capture unwanted contaminants from a flowing fluidcoming in direct contact with the composite surface.

In one embodiment, the present invention includes incorporating acontaminant-capturing filler into a composite material such as theincorporation of the filler results in a multi-functional compositematerial. The multi-functional composite material provides all of thebenefits of a composite article with the additional benefit of beingable to capture contaminants. For example, in one preferred embodiment,the present invention is directed to a method of manufacturing afiber-reinforced composite article for radionuclide removal. Thefiber-reinforced composite material utilizes a contaminant removalprocess embedded within the composite material very near the surface ofthe formed composite article which is in contact with the contaminant.The unique method of manufacture of the present invention can beutilized in a wide variety of different applications and processes formaking composite articles, including for example infusion, pultrusion,filament winding, and other similar processes. In one specificembodiment, the manufacturing method of the present invention can beused for manufacturing a multi-layer composite pipe article of apredetermined number of layers and of a predetermined inner diameter.

For example, in another preferred embodiment, the present inventionincludes the use of a filament winding method to manufacture a compositepipe structure that can be used in a piping application. However, thescope of fabrication of the present invention is not limited to only afilament winding process but may include any composite fabricationmethod and/or polymer matrix where composite articles can be made.However, the present invention manufacturing process is more complicatedthat simply using a filament winding operation to fabricate a pipe. And,the present invention described herein includes a multifunctionalcomposite material.

Terms used herein include the following:

“Fiber-free region” herein means a region of cured polymer matrix thatthat has no amount of fiber reinforcement material in the polymermatrix.

“Fiber-rich region” or “fiber-reinforced region” herein means a regionof cured polymer matrix that contains an amount of fiber reinforcementmaterial in the polymer matrix.

“Contiguous boundary of a non-delineated width” herein means aqualitative interfacial region between the fiber-free region andfiber-rich region, wherein the interfacial region is of a non-measurablewidth and is chemically bonding the fiber-rich region and fiber-freeregion forming a homogeneous integral boundary region generally of across-section where the fiber-free region and fiber-rich region areintegrally in contact with one another via the boundary region.

“Radionuclide” herein means an isotope with an unstable nucleus,characterized by excess energy available to be imparted either to anewly created radiation particle within the nucleus or via internalconversion.

“Radionuclide removal” herein means the transfer of the unstable nucleusdescribed above from an undesired location to a desired location.

The present invention incorporates (imbeds), for example, a radionuclideremoval mechanism (e.g., in the form of BaSO₄ crystals or particles)into a fiber-reinforced composite pipe manufacturing method through theuse of a two-step manufacturing process (gel layer production and thenfilament winding) resulting in a light-weight fiber-reinforced compositepipe product adapted for contaminant capture without the need for aseparate coating layer. Furthermore, the pipe with the contaminantremoving layer is manufactured substantially simultaneously; and thediameter of the pipe is not limited to a specific diameter, i.e., thepipe can be made to have a wide or a very narrow diameter. Thecapability to adjust a pipe's diameter is advantageous because a narrowdiameter pipe can be used instead of a pipe with a thick metalprotective layer even for high pressure situations (for examplehydraulic fracturing). By having radium capture occur on the compositepipe itself, i.e., downwell rather than above ground, this can eliminateor lessen the need for an above-the-ground treatment of the water andother fluids coming out of the well.

With reference to FIG. 1, there is shown a fiber-reinforced compositearticle, in this case a cylindrical member such as a conduit or pipestructure, generally indicated by numeral 10 with an internal space 11of a predetermined diameter. The cylindrical pipe structure 10 of FIG. 1is prepared by integrally bonding an original first polymer fiber-freelayer and an original second polymer fiber-rich layer. And, upon bondingthe original first polymer fiber-free layer to the original secondpolymer fiber-rich layer, a single body or layer containing at leastthree distinct regions is formed, i.e., the overall construction of thefiber-reinforced composite article includes: (1) a first polymerfiber-free region 12; (2) a second polymer fiber-rich region 13; and (3)a third polymer boundary region 14. The above three regions 12, 13, 14form the overall single body or layer, generally indicated by numeral15, comprising the fiber-reinforced composite article 10 having theabove three distinct regions. The boundary region 14 originatesnaturally as a result of curing the original first polymer fiber-freelayer to the original second polymer fiber-rich layer

The fiber-reinforced composite 10, such as pipe member 10, is useful forremoving contaminants present in a liquid fluid when the liquid fluidflows through the interior space 11 of the pipe member 10 and the fluidcomes into contact with the first polymer fiber-free region 12 of thecomposite. The mechanism for removing contaminants is built into thecomposite structure which includes the first polymer fiber-free region12 containing a material adapted for removing contaminants such asparticles 16. The contaminant-removing particles 16 are integrated intothe first polymer fiber-free region 12; and are integrally embedded inthe polymer of the first polymer fiber-free region 12. The first polymerfiber-free region 12 preferably contains only particulate material 16and no fibers 17 are contained in the fiber-free region 12.

The second polymer fiber-rich region 13 contains fiber reinforcementmaterial 17 such continuous or discontinuous fibers 17. The fibers 17are integrated into the second polymer fiber-rich region 13; and areintegrally embedded in the polymer of the second polymer fiber-richregion 13. The second polymer fiber-rich region 13 preferably containsonly fibers 17 and no particles 16 are contained in the fiber-richregion 13.

As aforementioned, upon bonding the outer surface of the first polymerfiber-free region and the inner surface of the second polymer fiber-richregion, a third polymer boundary region 14 is formed. The outer surfaceof the first polymer fiber-free region 12 is integrally bonded to theinner surface of the second polymer fiber-rich region 13 forming thethird polymer boundary region 14 disposed between the first polymerfiber-free region 12 and the second polymer fiber-rich region 13 asshown in FIG. 1. As a result of bonding, the third polymer boundaryregion 14 contains a portion of the first polymer fiber-free region 12having the particles 16 and a portion of the second polymer fiber-richregion 13 having the fibers 17. By its nature, the third polymerboundary region 14 comprises a contiguous boundary of a non-delineatedwidth and a non-delineated boundary line between the first polymerfiber-free region 12 and the second polymer fiber-rich region 13; thatis, the first polymer fiber-free region is integrally attached to thesecond polymer fiber-rich region such that the first polymer fiber-freeregion and second polymer fiber-rich region are infused together formingthe third polymer boundary region 14 comprising a polymer matrix infusedwith some fibers and some contaminant-capturing particles intermingledwith each other.

In FIG. 2, there is shown a micrograph at 5× magnification of part ofthe pipe structure of FIG. 1, generally indicated by numeral 20,including a first polymer fiber-free region 21 integrally bonded to asecond polymer fiber-rich region 22 forming a third polymer boundaryregion 23 disposed somewhere between the dotted lines labeled A and B;and between the first polymer fiber-free region 21 and the secondpolymer fiber-rich region 22.

In FIG. 3, there is shown a micrograph at 10× magnification of part ofthe pipe structure of FIG. 1, generally indicated by numeral 30,including a first polymer fiber-free region 31 integrally bonded to asecond polymer fiber-rich region 32 forming a third polymer boundaryregion 33 disposed somewhere between the dotted lines labeled D and E;and between the first polymer fiber-free region 31 and the secondpolymer fiber-rich region 32. The inner surface of the first polymerfiber-free region 31 forms the outer perimeter of internal space 34(shown as dotted line F) of a pipe. In FIG. 3 again, there is shown theparticles 35 embedded in the first polymer fiber-free region 31; and thefibers 36 embedded in the second polymer fiber-rich region 32.

With reference to FIG. 1 again, there is shown a composite structure 10,such as a pipe structure 10 and the inner space of the pipe structure isindicated by numeral 11. The diameter of the space 11 can be, but is notlimited to, generally from about 3 mm to about 300 mm in one embodiment,from about 6 mm to about 250 mm in another embodiment, and from about 10mm to about 200 mm in still another embodiment. The diameter of thespace 11 can vary depending on the application in which the pipe will beused. For example, piping used for a hydraulic fracturing process isgenerally in the range of from about 20 mm to about 200 mm in diameter.

Another embodiment of a composite pipe structure is shown in FIG. 4. Thecomposite pipe structure, generally indicated by numeral 40, includes amulti-layer construction including optional additional layers and/oroptional regions. For example, the pipe 40 may include a first polymerfiber-free gel layer 41 containing a particulate material for removingcontaminants 47 such as barium sulfate, an outside second polymerfiber-rich composite layer 42 containing fibers 48, a glass veil 43, anda release film or layer 44, all disposed on the outer surface of aninner mandrel 45 (e.g., made of HDPE) with internal space 46. Any numberof other optional layers can be added to the composite structure 40depending on the enduse of the final composite pipe product.

With reference to FIG. 4 again, the first polymer fiber-free gel layer41 of the composite article 40 may be made of any conventional curablepolymer resins including for example bisphenol-A-based resins,bisphenol-F-based resins, and other known epoxides and curable(thermosetting) resins; and mixtures thereof. The gel layer 41 may alsoinclude other additives such as monofunctional reactive diluents(including for example cresyl glycidyl ether, butyl glycidyl ether, andthe like), di-functional reactive diluents (including for examplebutanediol digylcidyl ether, butane dioxide, and the like), non-reactivediluents (including for example dibutyl phthalate and phenolic compoundsand the like), fillers (including for example carbon black, titaniumdioxide, and the like), and mixtures thereof.

Additionally, a curing agent is used in the first polymer fiber-free gellayer 41 to react with the first polymer to form the cross-linked firstpolymer network. The curing agent (also known as a hardener orcrosslinking agent) may include for example polyamides, polyamidoamines,phenols, amino-formaldehydes, carboxylic acid functional polyesters,anhydrides, polysulfides, polymercaptans, and mixtures thereof.

The first polymer fiber-free gel layer 41 also includes particulatematerial for removing contaminants such as barium sulfate particulate 47dispersed in the first polymer fiber-free gel layer 41. Other particles47 that can be dispersed and embedded in the first polymer fiber-freegel layer 41 may include for example barium sulfate particles with adiameter of from about 1 μm to about 5 μm.

The amount of particles 47 present in the first polymer fiber-free gellayer 41 may be generally from about 10% by weight to about 95% byweight in one embodiment, from about 20% by weight to about 90% byweight in another embodiment, and from about 30% by weight to about 85%by weight in still another embodiment.

In one preferred embodiment, the first polymer fiber-free gel layer 41may be include a bisphenol-A-based epoxy resin as the first polymer, anamine curing agent, and barium sulfate particulate.

One of the beneficial properties of the gel layer 41 is the capabilityof the gel layer 41 to remove contaminants such as radionuclide from aliquid fluid coming into contact with the gel layer 41. “Fiber-free”with reference to the amount of fibers 48 present in the gel layer 41means there is less than 15% by weight amount of fibers in the gel layer41 and preferably zero.

The first system or formulation for making the first polymer fiber-freegel layer 41, is designed to have an initial viscosity of at least20,000 mPa-s to prevent sagging and dripping when the gel layer 41 isapplied to the mandrel 45; and the formulation is designed to have a geltime of approximately (˜) 20 minutes. For example the gel layer 41 mayhave an initial viscosity of generally from about 10,000 mPa-s to about40,000 mPa-s in one embodiment, from about 15,000 mPa-s to about 30,000mPa-s in another embodiment, and from about 18,500 mPa-s to about 25,000mPa-s in still another embodiment. For example the gel layer 41 may havea gel time of generally from about

5 minutes (min) to about 45 min in one embodiment, from about 10 min toabout 30 min in another embodiment, and from about 15 min to about 25min in still another embodiment.

The thickness of the gel layer 41 of the composite article structure 40can be generally from about 0.25 millimeters (mm) to about 5 mm in oneembodiment, from about 0.5 mm to about 3 mm in another embodiment, andfrom about 1 mm to about 2 mm in still another embodiment. A gel layer41 that is too thin (i.e., less than about 0.25 mm) may not provideenough coverage to the inside of a pipe member and will result in anunderperforming part with less contaminant capture than desired. A gellayer 41 that is too thick (i.e., greater than about 0.5 mm) can resultin adverse processing issues such as gel-layer dripping and waste.

In the embodiment shown in FIG. 1, the gel layer 12 is bonded to thecomposite layer 13 forming a bonding region 14. In a preferredembodiment, shown in FIG. 4, the gel layer 41 of the composite articlestructure 40 of the present invention is disposed in between a veillayer 43 and a release layer 44; and the second polymer fiber-richcomposite layer 42 is disposed on the outer surface of the veil layer43.

As shown in FIG. 4, outer surface of the gel layer 41 is disposed incontact with and adjacent to the inner surface of the glass veil layer43; and the inner surface of the gel layer 41 is disposed in contactwith and adjacent to the outer surface of a release layer 44. Therelease layer 44, with the inner surface of the release film or layer 44disposed on the outer surface of the mandrel 45, is used to avoid thecomposite pipe structure from sticking to the mandrel 45.

The second polymer fiber-rich composite layer 42 of the compositearticle 40, shown in FIG. 4, may be made of any of the conventionalpolymer resins described above with reference to the first polymerfiber-free composite layer 41. The polymer resin used to manufacture thesecond polymer fiber-rich composite layer 42 can be the same ordifferent than the polymer resin used to manufacture the first polymerfiber-free composite layer 41.

Additionally, a curing agent is used in the second polymer fiber-richcomposite layer 42 to react with the second polymer to form thecross-linked second polymer network.

The second polymer fiber-rich composite layer 42 also includes afiber-reinforcement which can be for example continuous fiber ordiscontinuous fiber. The fibers 48 in the polymer matrix of thecomposite layer 42 may be of different origins, including but notlimited to, carbon fibers (including for example pitch based andpolyacrylonitrile based), glass fibers (including for example e-glass,s-glass, and the like), aramid fibers, natural fibers, and mixturesthereof. The fibers can be applied in any direction in athree-dimensional coordinate frame that is consistent with theorydictating a functioning laminate structure.

The amount of fibers 48 present in the second polymer fiber-richcomposite layer 42 may be generally from about 50% by weight to about85% by weight in one embodiment, from about 60% by weight to about 80%by weight in another embodiment, and from about 65% by weight to about70% by weight in still another embodiment.

The thermosetting or thermoplastic resin used as the second polymermatrix of the composite layer 42 preferably has a suitable viscosity toachieve homogenous fiber bundle impregnation during a specifiedresidence time dictated by the particular individual process used (forexample, in a filament winding process, the residence time is the timethe fiber bundle spends in the impregnation bath). For example, in apreferred embodiment, the composite layer 42 may be made of continuousfiber rovings and a thermosetting resin matrix such as an epoxy resin.Alternatively, the composite layer 42 may comprise a continuous fiberroving and a thermoplastic matrix. The thermoplastic matrix can be forexample polypropylene, polysulfone, polyether ether ketone and the like;and mixtures thereof.

One of the beneficial properties of the composite layer 42 is that thelayer 42 is free of the radionuclide capturing particle material 47 andexhibits a homogenous laminate structure (i.e., the composite layer 42is free of defects, for example less than about 5% by weight [defects]).“Free of particles” with reference to the amount of particles 47 in thecomposite layer 42 means there is less than 10% by weight amount ofparticles in the composite layer 42 and preferably zero.

In one embodiment, the composite layer 42 of the composite articlestructure 40 of the present invention is disposed on the outer surfaceof the veil layer 43. As shown in FIG. 4, the layer 42 is disposed incontact with and adjacent to the outside surface of the veil layer 43.For example, the composite layer 42 may be laid on the top surface ofthe veil layer 43 and then all of the layers of the article 40 can bechemically bonded into the polymer matrix together during the curingprocess.

The thickness of the composite layer 42 of the composite articlestructure 40 is not limited to a predetermined thickness. However, thethickness of the composite layer 42 can be generally from about 0.25 mmto about 100 mm in one embodiment, from about

1 mm to about 60 mm in another embodiment, and from about 5 mm to about40 in still another embodiment.

The veil layer 43 of the composite article 40, shown in FIG. 4, may bemade of various materials including for example glass, polyester,carbon, or mixtures thereof. For example, in a preferred embodiment, theveil layer 43 may be made of e-glass.

One of the beneficial properties of the veil layer 43 is to provide aseparating layer such that a more defined boundary can be establishbetween the first polymer fiber-free region containing a radionuclideremoval mechanism and the second polymer fiber-rich region containingfiber reinforcement which provides mechanical strength to article 40.

In one embodiment, the veil layer 43 of the composite article structure40 of the present invention is laid in between the composite layer 42and the gel layer 41. As shown in FIG. 4 the veil layer 12 is disposedin contact with and adjacent to the inner surface of the composite layer42; and in contact with and adjacent to the outer surface of the gellayer 41.

The thickness of the veil layer 43 of the composite article structure 10can be generally from about 8 μm to about 100 μm in one embodiment, fromabout 10 μm to about 75 μm in another embodiment, and from about 15 μmto about 50 μm in still another embodiment.

The release film layer 44 of the composite article 40, shown in FIG. 4,may be made of any material that is suitable for providing anadvantageous release mechanism for releasing the composite article 40from the mandrel 45. In a preferred embodiment for example, the releasefilm layer 44 may be made of paste waxes, liquid polymers, polyvinylalcohols (PVA's) or semi-permanents.

In one embodiment, the release film layer 44 of the composite articlestructure 40 of the present invention is disposed in between the gellayer 41 and the inner mandrel 45. As shown in FIG. 4, the release filmlayer 44 is disposed in contact with and adjacent to the inner surfaceof the gel layer 41; and the release film layer 44 is disposed incontact with and adjacent to the outer surface of the mandrel 45.

The thickness of the release film layer 44 of the composite articlestructure 40 can be generally from about 0.01 mm to about 2 mm in oneembodiment, from about 0.05 mm to about 1 mm in another embodiment, andfrom about 0.1 mm to about 0.5 mm in still another embodiment.

The inner mandrel 45, shown in FIG. 4, may be made of for example anyconventional material with properties adapted to withstand the operatingand curing conditions of the process of the present invention. Forexample, the inner mandrel 45 may be made of stainless steel, carbonsteel, aluminum, iron and thermoplastics (including for examplepolyether ether ketone, high-density polyethylene, and the like).

As shown in FIG. 4, the outer surface of the mandrel 45 useful in thepresent invention is disposed in contact with and adjacent to the innersurface of the release film layer 44. The mandrel 45 only needs to bethick enough to support applied layers throughout the processing of thecomposite article 40. Depending on the material used, the thickness ofthe mandrel 45 can vary. Other considerations for the thickness of themandrel 45 can include processing speed, curing temperatures, and typeof resins used in the process. For example, the thickness of the innermandrel 45 of the composite article structure 40 can be generally fromabout 3 mm to about 300 mm in one embodiment, from about 6 mm to about250 mm in another embodiment, and from about 10 mm to about 200 mm instill another embodiment.

The structure 40 of FIG. 4 is shown with a number of layers to form amulti-layer construction. However, the number of layers for thestructure 40 is not limited to the layers as shown in FIG. 4. Any numberof layers can make up the overall multi-layer structure 40. For examplethe number of layers can be generally from about 2 layers to about 15layers in one embodiment, from about 3 layers to about 10 layers inanother embodiment, and from about 4 layers to about 8 layers in stillanother embodiment. In a preferred embodiment, the minimum number oflayers that can be used to manufacture the composite structure 40 can befor example three layers: (1) a first polymer fiber-free gel layer, (2)a veil layer, and (3) a second polymer fiber-rich layer.

The overall diameter of the pipe structure 40 with the multi-layerconstruction as shown in FIG. 4 can also vary depending on theapplication in which the pipe structure 40 will be used. However, theoverall diameter of structure 40 can be generally from about 5 mm toabout 400 mm in one embodiment, from about 20 mm to about 300 mm inanother embodiment, and from about 30 mm to about 200 mm in stillanother embodiment.

The composite product or article, such as a pipe, prepared by theprocess of the present invention exhibits unexpected and uniqueproperties. In one embodiment for example, the overall fabricatedcomposite article can weigh less than a similar conventional metal partperforming the same function. For example, the composite of the presentinvention can weigh less than a metal counterpart part generally lessthan about 5% to about 75% in one embodiment, less than about 10% toabout 60% in another embodiment, and less than about 15% to about 50% instill another embodiment.

Another broad scope of the present invention includes a process formanufacturing a fiber-reinforced composite article for radionuclideremoval. The process includes manufacturing a composite article bybonding at least two polymer layers to form a single composite articlecontaining at least one first polymer fiber-free region, at least asecond polymer fiber-rich region, and a third boundary region disposedbetween (separating) the first polymer fiber-free region and the secondpolymer fiber-rich region. The system, composition, or formulation,includes components to manufacture: (a) a first polymer fiber-freeregion containing contaminant-removing particles such as radionuclideremoval particles; and components to manufacture: (b) a second polymerfiber-rich region containing fiber reinforcement material.

The fiber-free polymer region containing a contaminant-capturingmaterial such as radionuclide-removal particles comprises the gel layerof the composite. The composition used to form the gel layer of thecomposite includes for example, the following compounds or components:(i) an epoxy resin such as a novolac type epoxy resin, (ii) a curingagent such as an amine curing agent for curing the epoxy resin, and(iii) a contaminant-capturing particulate material such as BaSO₄. Theabove gel layer composition can also include (iv) a dispersing aid(e.g., BYK-940) for homogenously dispersing the above componentsthroughout the fiber-free polymer region, particularly for dispersingthe above particulate material into the fiber-free polymer region.

In one embodiment, the first formulation is applied as a gel layer andis designed to have a high (e.g., >than about 20,000 mPa-s) initialviscosity, to prevent sagging and dripping, and to have a fast gel time(e.g., <1 hour at 25° C.). For example, the viscosity of the firstformulation to form the gel layer can generally be from about 20,000mPa-s to about 80,000 mPa-s in one embodiment, from about 30,000 mPa-sto about 60,000 mPa-s in another embodiment, and from about 40,000 mPa-sto about 55,000 mPa-s in still another embodiment. If the viscosity ofthe gel layer resin formulation is less than the described viscositiesthe gel layer will have a tendency to sag or drip off the mandrel usedin the winding process and may lead to inhomogeneous distribution of thecontaminant removal mechanism in the inner layer of the composite pipe.If the viscosity of the gel layer resin formulation is greater than thedescribed viscosities then the mixed formulation may be too viscous toapply and may lead to inhomogeneous distribution of the contaminantremoval mechanism in the inner layer of the composite pipe.

For example, the gel time of the first resin formulation can generallybe from about 2 minutes to about 50 minutes in one embodiment, fromabout 3 minutes to about 30 minutes in another embodiment, and fromabout 5 minutes to about 20 minutes in still another embodiment. If thegel time of the resin formulation is too short, then the application ofthe gel layer will become very difficult and adequate bonding may not beachieved between the fiber-free region and fiber-rich region.

The epoxy resin used to form the gel layer can include, for example, abisphenol-A-based resin, a bisphenol-F-based resin, other thermosettingresins, and mixtures thereof. The formulation for forming the gel layermay also contain other optional compounds such as a monofunctionalreactive diluent (including for example, cresyl glycidyl ether, butylglycidyl ether, and the like.), a di-functional reactive diluent(including for example butanediol digylcidyl ether, butane dioxide, andthe like.), a non-reactive diluent (including for example dibutylphthalate and phenolic compounds), a filler (including for examplecarbon black, titanium dioxide, and the like.); and mixtures thereof.

In a preferred embodiment, the epoxy useful in the process of thepresent invention may include for example, one or more bisphenol-A-basedresins, bisphenol-F-based resins, and mixtures thereof.

One of the beneficial properties of the epoxy resin used in the presentinvention is its initial viscosity as specified in the ranges describedabove so that dripping of the mixed resin formulation off the mandreldoes not occur.

The curing agent used to cure the epoxy resin present in the gel layercan include, for example, an amine, a polyamide, a polyamidoamine, aphenol, an amino-formaldehyde, a carboxylic acid functional polyester,an anhydride, a polysulfide, a polymercaptan; and mixtures thereof.

In a preferred embodiment, the curing agent useful in the process of thepresent invention may include for example, one or more aliphatic amines,cycloaliphatic amines, polyetheramines, and mixtures thereof.

One of the beneficial properties of the curing agent is a low equivalenthydrogen weight (no greater than 60 amine hydrogen equivalent weight[AHEW]) so that only a small amount of the amine curing agent is needed.A high hydrogen equivalent weight will need a large amount of curingagent and will decrease the viscosity of the gel-layer so that it isun-usable.

The particulate material added to the gel layer can include, forexample, any particulate in a micro or nanoscale size that isadvantageous for capturing contaminants and removing the contaminantsfrom a contaminated liquid fluid such as radionuclides where theparticulate and contaminant come into direct contact with one another inthe fiber-free region containing contaminant-capturing particles. Forexample, the contaminant-capturing particulate material may includebarium sulfate (BaSO₄).

The contaminant-capturing particulate used in the present invention mayinclude, for example, metal-sulfates, metal oxides, and/or anycombination thereof. The contaminant-capturing particles are solid atroom temperature. The contaminant-capturing particulate may have amelting point greater than 500° C., greater than 800° C., and/or greaterthan 1000° C. The melting point of the contaminant-capturing particulatemay be less than 2500° C. Exemplary metal-sulfates include alkalimetal-sulfates and alkaline earth metal-sulfates. Exemplarymetal-sulfates include barium sulfate, strontium sulfate, and mixturesthereof. In one preferred embodiment, the contaminant-capturingparticulate is barium sulfate. Exemplary metal oxides include manganeseoxides such as manganese(II) oxide (MnO), manganese(II,III) oxide(Mn₃O₄), manganese(III) oxide (Mn₂O₃), manganese dioxide (MnO₂), andmanganese(VII) oxide (Mn₂O₇). Exemplary manganese oxide based mineralsinclude birnessite, hausmannite, manganite, manganosite, psilomelane,and pyrolusite.

The contaminated liquid that is processed using a fiber-reinforcedcomposite article of the present invention may include, for examplewater, brine, a blend of crude oil and water, or a blend of crude oiland brine.

In a preferred embodiment, the particulate material useful in theprocess of the present invention may include for example, one or moreforms, shapes or sizes of barium sulfate (BaSO₄). One of the beneficialproperties of the particulate material includes the capability of theparticulate material to capture and entrap a radionuclide by theradionuclide coming into direct contact with the particulate material.

The concentration of the particulate material used in the presentinvention may range generally from about 5 wt % to about 90 wt % in oneembodiment, from about 15 wt % to about 85 wt % in another embodiment,and from about 25 wt % to about 80 wt % in still another embodiment. Ifthere is too little particulate material in the gel layer, there may notbe sufficient material to capture the contaminant of interest. If thereis too much particulate material in the gel layer, inter-layer andintra-layer bonding may not be sufficient to form a homogenous article.

The dispersing aid added to the gel layer can include, for example, anyadditive that decreases settling of additives for contaminant removal.In a preferred embodiment, the dispersing aid useful in the process ofthe present invention may include for example, one or more polysiloxanecopolymer that decreases settling of inorganic additive for radionuclideremoval.

One of the beneficial properties of the dispersing aid is its ability tokeep the particle for radionuclide removal from settling in thegel-layer.

The concentration of the dispersing aid used in the present inventionmay range generally from about 0 wt % to about 2 wt % in one embodiment,from about 0.25 wt % to about 1.5 wt % in another embodiment, and fromabout 0.5 wt % to about 1 wt % in still another embodiment. The use oftoo little dispersing aid will lead to inefficiently dispersedparticles. The use of too much dispersing aid will affect theperformance of the contaminant removal mechanism.

Optional additives that can be added to the formulation for forming thegel layer may include for example monofunctional reactive diluents(including for example cresyl glycidyl ether, butyl glycidyl ether, andthe like.), di-functional reactive diluents (including for examplebutanediol diglycidyl ether, butane dioxide, and the like), non-reactivediluents (including for example dibutyl phthalate and phenoliccompounds) useful for modifying the viscosity of the gel layer such thatadvantageously the gel layer can be processed through the process of thepresent invention.

The concentration of the optional additives used in the presentinvention may range generally from 0 wt % to about 5 wt % in oneembodiment, from about 0.1 wt % to about 3 wt % in another embodiment,and from about 0.5 wt % to about 1 wt % in still another embodiment. Iftoo much viscosity modifier is used (e.g., >5 wt %), the mechanicalproperties of the formulation may be adversely impacted.

In one embodiment, an accelerator may be used as an optional additivethat can be added to form the gel layer. For example, a gel or cureaccelerator useful for accelerating the rate of crosslinking within thecuring formulation may be used.

The concentration of the optional accelerator used in the presentinvention may range generally from 0 wt % to about 3 wt % in oneembodiment, from about 0.1 wt % to about 2 wt % in another embodiment,and from about 0.5 wt % to about 1 wt % in still another embodiment. Iftoo much gel or cure accelerator is added to the gel layer formulation,then the formulation may be too reactive and a homogenous gel layer maynot be achieved.

Another optional additive that can be added to form the gel layer mayinclude for example fillers (including for example carbon black,titanium dioxide, and the like) useful for providing advantageousproperties that the gel layer could not achieve without such as athermal barrier, wear reduction barrier and the like.

The concentration of the filler used in the present invention may rangegenerally from 0 wt % to about 25 wt % in one embodiment, from about 0.1wt % to about 15 wt % in another embodiment, more preferably from about0.5 wt % to about 10 wt % in still another embodiment. If too muchfiller beyond the above concentrations is added to the formulation, thenthe formulation may be too reactive and a homogenous gel-layer may notbe achieved. If too little filler outside the ranges above is used, thanthe desired properties achieved through incorporation of the filler maynot be achieved.

The second polymer fiber-rich or fiber-reinforced region of thecomposite is formed using a composition, system or formulationcontaining the following compounds or components: (i) a polymer resin,(ii) a curing agent for curing the resin, and (iii) a fiberreinforcement material.

The second formulation which can be used in the present invention mayinclude a conventional formulation for filament winding with lowviscosity (for example, from about 350 mPa-s to about 600 mPa-s) forhomogenous fiber bundle impregnation and long gel times (for example, >6hours at 25° C.). For example, the viscosity of the second formulationcan generally be from about 200 mPa-s to about 1000 mPa-s in oneembodiment, from about 300 mPa-s to about 800 mPa-s in anotherembodiment, and from about 350 mPa-s to about 600 mPa-s in still anotherembodiment. The viscosity of the formulation needs to be in accordancewith a traditional filament winding system. Too high a viscosity willresult in poor fiber bundle impregnation. Too low a viscosity willresult in resin drainage from the fiber bundle.

It is desired to achieve homogenous fiber bundle impregnation such thatthe resulting structure will perform as designed without any deleteriousamount of wet out of the resin formulation as can be determined bytechniques known in the art. For example, the gel time of the secondformulation can generally be from about 1 hour (hr) to about 16 hr inone embodiment, from about 2 hr to about 12 hr in another embodiment,and from about 4 hr to about 8 hr in still another embodiment. If thegel time is too short, the entire composite structure may not be formedbefore the curing reaction occurs, leading to a heterogeneous laminatestructure. There are no major consequences to having too long a gel timebeyond the 16 hours discussed about other than the process would beuneconomical and inefficient.

The polymer resin used to form the fiber-rich (fiber-reinforced) layercan include, for example, a bisphenol-A-based resin, a bisphenol-F-basedresin, a monofunctional reactive diluent (including for example, cresylglycidyl ether, butyl glycidyl ether, and the like.), di-functionalreactive diluents (including for example, butanediol digylcidyl ether,butane dioxide, and the like.), non-reactive diluents (including forexample, dibutyl phthalate and phenolic compounds), fillers (includingfor example, carbon black, titanium dioxide, and the like.), andmixtures thereof. Additionally, a curing agent is used to form thecross-linked polymer network that may be comprised of polyamides,polyamidoamines, phenol and amino-formaldehydes, carboxylic acidfunctional polyesters, anhydrides and polysulfides and polymercaptans;and mixtures thereof.

In a preferred embodiment, the polymer resin useful in the process ofthe present invention may include for example, one or morebisphenol-A-based resins, one or more di-functional reactive diluents,and mixtures thereof.

One of the beneficial properties of the polymer resin of the secondformulation is its low initial viscosity, (i.e., the formulation whichincludes the resin, additives, fillers and curing agent). For example,the initial viscosity of the formulation can be from about 350 mPa-s toabout 600 mPa-s.

The concentration of the polymer resin used in the present invention mayrange generally from about 60 wt % to about 99 wt % in one embodiment,from about 70 wt % to about 90 wt % in another embodiment, and fromabout 80 wt % to about 85 wt % in still another embodiment. Use of toomuch reactive diluent (and therefore reducing the amount of epoxy resinin the overall formulation to below 60 wt %) will significantly andadversely impact the thermal and mechanical properties of the finalcured composite article.

The curing agent used to cure the polymer resin present to form thefiber-reinforced polymer region can include, for example, any of thecuring agents described above with reference to the gel layer. Forexample, the curing agent can be an amine, a polyamide, apolyamidoamine, a phenol, an amino-formaldehyde, a carboxylic acidfunctional polyester, an anhydride, a polysulfide, a polymercaptan; andmixtures thereof.

In a preferred embodiment, the curing agent useful in the process of thepresent invention may include for example, one or more aliphatic amines,cycloaliphatic amines, polyetheramines, and mixtures thereof.

The reinforcement material used to form the fiber-rich region layer caninclude, for example, discontinuous or continuous glass fibers (e.g.,e-glass, s-glass, and the like), carbon fibers (e.g., polyacrylonitrile[PAN] fibers and pitch based fibers), aramid fibers, natural fibers, andmixtures thereof.

In a preferred embodiment, the reinforcement material useful in theprocess of the present invention may include for example, one or morecontinuous or discontinuous glass fibers, continuous or discontinuouscarbon fibers, and mixtures thereof.

The concentration of the reinforcement material used in the presentinvention may range generally from about 10 wt % to about 90 wt % in oneembodiment, from about 15 wt % to about 85 wt % in another embodiment,and from about 20 wt % to about 80 wt % in still another embodiment. Thereinforcing material needs to have such a presence that the compositearticle meets electrical, thermal and mechanical performance targets forthe industry. Too low or too high an amount of reinforcing material willcause detrimental issues in the aforementioned performances.

A beneficial optional additive that can be added to form the gel layermay include for example monofunctional reactive diluents (including forexample cresyl glycidyl ether, butyl glycidyl ether, and the like),di-functional reactive diluents (including for example butanedioldigylcidyl ether, butane dioxide, and the like), non-reactive diluents(including for example dibutyl phthalate and phenolic compounds, and thelike) which is capable of modifying the viscosity of the gel-layer to beadvantageous for processing.

The concentration of the optional additive, when used in the presentinvention, may range generally from 0 wt % to about 5 wt % in oneembodiment, from about 0.1 wt % to about 3 wt % in another embodiment,from about 0.5 wt % to about 1 wt % in still another embodiment. If toomuch viscosity modifier is used (e.g., >5 wt %), the mechanicalproperties of the formulation may be adversely impacted.

A beneficial optional additive that can be added to form the gel layermay include for example a gel or a cure accelerator which is adapted toaccelerating the rate of crosslinking within the curing formulation.

The concentration of the optional additives used in the presentinvention may range generally from 0 wt % to about 3 wt % in oneembodiment, from about 0.1 wt % to about 2 wt % in another embodiment,and from about 0.5 wt % to about 1 wt % in still another embodiment. Iftoo much gel or cure accelerator is added then the formulation may betoo reactive and a homogenous gel-layer may not be achieved.

In general, the process for manufacturing a fiber-reinforced compositearticle useful for contaminant removal such as radionuclide removalincludes the steps of:

(A) disposing a gel material layer onto the surface of a mandrel; (B)introducing a fiber reinforcement into a polymer resin impregnationmeans; (C) impregnating the fiber reinforcement of step (B) with apolymer resin to form a polymer fiber-reinforced layer material; (D)disposing the resin impregnated fiber-reinforced layer material of step(C) onto the surface of the gel material layer of (A); and (E) bondingpolymer gel material layer to the polymer fiber-reinforced layermaterial by curing the combination of the gel material layer and theresin impregnated fiber-reinforced layer material to form at least onesingle layer of a fiber-reinforced composite including at least threeregions in said at least one single layer. The three regions include thefollowing:

-   -   (a) at least one first polymer fiber-free region containing        material adapted for removing contaminants, the contaminant        removal material integrated into the first polymer fiber-free        region;    -   (b) at least one second polymer fiber-rich region containing        fiber reinforcement material; and    -   (c) at least one third polymer boundary region containing a        portion of the first polymer fiber-free region and a portion of        the second polymer fiber-rich region.

The first polymer fiber-free region includes an inner surface and anouter surface; and the second polymer fiber-rich region includes aninner surface and an outer surface. The outer surface of the firstpolymer fiber-free region is integrally bonded to the inner surface ofthe second polymer fiber-rich region forming the at least one thirdpolymer boundary region disposed between the first polymer fiber-freeregion and the second polymer fiber-rich region. The third polymerboundary region further comprises a contiguous boundary of anon-delineated width between the first polymer fiber-free region and thesecond polymer fiber-rich region. And, the first polymer fiber-freeregion is integrally attached to the second polymer fiber-rich regionsuch that the first polymer fiber-free region and second polymerfiber-rich region are infused together forming the at least one thirdpolymer boundary region.

More specifically, the first step of the process includes admixing therequired components to make the gel layer such as for example: (i) anepoxy resin, (ii) a curing agent such as an amine curing agent forcuring the epoxy resin, (iii) a particulate material; and

(iv) any optional compounds, for example, a dispersing aid. Then themixture can be processed under conditions for forming a gel layerincluding heating the above mixture at a predetermined temperature andtime to form an effective gel layer. The temperature of heating cangenerally be in the range of from about 15° C. to about 60° C. in oneembodiment, from about 20° C. to about 40° C. in another embodiment, andfrom about22° C. to about 30° C. in still another embodiment. If the temperatureof the formulation is too low, this may cause a significant increase inviscosity (e.g., >40,000 mPa-s) resulting in an inability to process thegel layer onto the mandrel. If the temperature of the formulation is toohigh, this may case a significant increase in the reactivity of the gellayer and may not allow sufficient time to apply the gel layer to themandrel before curing.

The heating time to form the gel layer may be, for example, generallyfrom about 5 min to about 120 min in one embodiment, from about 10 minto about 60 min in another embodiment, and from about 15 min to about 45min in still another embodiment. In general, the heating time for thegel layer will depend on the composition and reactivity of the gellayer. Too high of a heating time may increase the temperature such thatthe curing reaction is induced and the gel layer cannot be properlyapplied to the mandrel. Too low of a heating temperature and theviscosity of the gel layer formulation may be too high such that the gellayer may not be homogenously applied to the mandrel.

The process of the present invention for forming the gel layer may be abatch process, an intermittent process, or a continuous process usingequipment well known to those skilled in the art.

Once the composition for the gel layer is made, the gel layerformulation is applied to the mandrel of a filament winding process.

The process includes the step of admixing the compounds or componentsrequired to make the second polymer fiber-rich composite layer of thecomposite: (i) a polymer resin, (ii) a curing agent for curing theresin, and (iii) a fiber reinforcement material. Then the mixture can beprocessed under conditions for forming a fiber-reinforced layergenerally including the steps of introducing a fiber reinforcement intoa polymer resin impregnation means; and impregnating the fiberreinforcement with a polymer resin to form a second polymerfiber-reinforced layer material.

Generally, to form the polymer fiber-reinforced layer, the impregnationof the fiber reinforcement with a polymer resin is carried out at apredetermined temperature and time to form an effectivefiber-reinforcement layer. The temperature of heating can generally bein the range of from about 15° C. to about 40° C. in one embodiment,from about 20° C. to about 35° C. in another embodiment, and from about25° C. to about 30° C. in still another embodiment. Any heating outsideof the above range may cause adverse effects to the desired rheologicalbehavior of the mixed formulation. For example, temperatures below 15°C. may cause the mixed formulation's viscosity to increase to a levelthat is un-usable in the methods described above as well as slowing theepoxy-amine reaction to such a low rate that the gel-point of thematerial cannot be reached. And, temperatures above 40° C. may lower theviscosity to such a state that the material will drip from the mandreland may not form a homogenous layer on the desired surface of thecomposite article. Additionally, a temperature higher than 40° C. mayprematurely induce the autocatalytic curing reaction and render themixed formulation un-usable.

If the composite article is heated for too little time, thecross-linking reaction associated with thermoset matrices may not becomplete with the resulting effect of producing an underperformingarticle.

The process of the present invention for forming the fiber reinforcedlayer may be a batch process, an intermittent process, or a continuousprocess using equipment well known to those skilled in the art. Theheating time to form the fiber reinforced composite may be, for example,generally from about 1 hour to about 24 hours in one embodiment, fromabout 1.5 hour to about 12 hours in another embodiment, and from about 2hours to about 8 hours in still another embodiment.

Upon bonding the combined fiber-reinforced layer and gel layer to form asingle composite article a first polymer fiber-free region, a secondpolymer fiber-rich region, and a third polymer boundary region is formedin the single composite article.

As aforementioned, the first polymer fiber-free region includes an innersurface and an outer surface; and the second polymer fiber-rich regionincludes an inner surface and an outer surface. The outer surface of thefirst polymer fiber-free region is integrally bonded to the innersurface of the second polymer fiber-rich region forming the at least onethird polymer boundary region disposed between the first polymerfiber-free region and the second polymer fiber-rich region. The thirdpolymer boundary region further comprises a contiguous boundary of anon-delineated width between the first polymer fiber-free region and thesecond polymer fiber-rich region. And the first polymer fiber-freeregion is integrally attached to the second polymer fiber-rich regionsuch that the first polymer fiber-free region and second polymerfiber-rich region are infused together forming the at least one thirdpolymer boundary region.

Some non-limiting examples of enduse applications for the compositeproduct of present invention may include, for example, in manufacturingan article by filament winding, pultrusion, infusion, hand lay-up, or acombination of such methods. The composite article can be for example aconduit, a pipe or piping for use in downhole wells in the oil and gasindustry; or a pipe for flowing a liquid fluid therein and removingcontaminants (e.g., a radionuclide) present in the liquid fluid from theliquid such as contaminated fluid from hydraulic fracturing operations.

Exemplary embodiments that may incorporate any or all of theabove-discussed features, include, the following:

A fiber-reinforced composite article useful for contaminant removalcomprising at least one single layer of a fiber-reinforced compositeincluding the following regions in said at least one single layer: (a)at least one first polymer fiber-free region containing material adaptedfor removing contaminants, said contaminant removal material integratedinto the first polymer fiber-free region; said first polymer fiber-freeregion including an inner surface and an outer surface; (b) at least onesecond polymer fiber-rich region containing fiber reinforcementmaterial; said second polymer fiber-rich region including an innersurface and an outer surface; and (c) at least one third polymerboundary region containing a portion of the first polymer fiber-freeregion and a portion of the second polymer fiber-rich region. Whereas,the outer surface of the first polymer fiber-free region is integrallybonded to the inner surface of the second polymer fiber-rich regionforming the at least one third polymer boundary region disposed betweenthe first polymer fiber-free region and the second polymer fiber-richregion; wherein the third polymer boundary region further comprises acontiguous boundary of a non-delineated width between the first polymerfiber-free region and the second polymer fiber-rich region; and whereinthe first polymer fiber-free region is integrally attached to the secondpolymer fiber-rich region such that the first polymer fiber-free regionand second polymer fiber-rich region are infused together forming the atleast one third polymer boundary region.

A process for manufacturing a fiber-reinforced composite article usefulfor contaminant removal at least one single layer of a fiber-reinforcedcomposite comprising the steps of: (i) providing a formulation forforming at least one first polymer fiber-free gel layer; (ii) applyingthe first polymer fiber-free gel layer formulation of (i) onto a mandrelof a filament winding process such that the polymer fiber-free gel layerformulation forms a polymer fiber-free gel layer of a predeterminedthickness on the mandrel; (iii) providing a formulation for forming atleast one second polymer fiber-rich layer; (iv) applying the secondpolymer fiber-rich layer formulation of (iii) onto the surface of thepolymer fiber-free gel layer produced in step (ii) such that the secondpolymer fiber-rich layer formulation forms a second polymer fiber-richlayer of a predetermined thickness disposed on the first polymerfiber-free gel layer which is disposed on the mandrel; and (v) curingthe first polymer fiber-free gel layer and second polymer fiber-richlayer to form at least one single layer of a fiber-reinforced composite;wherein the at least one single layer of a fiber-reinforced compositeincludes the following regions in said single layer: (a) at least onefirst polymer fiber-free region containing material adapted for removingcontaminants, said contaminant removal material integrated into thefirst polymer fiber-free region; said first polymer fiber-free regionincluding an inner surface and an outer surface; (b) at least one secondpolymer fiber-rich region containing fiber reinforcement material; saidsecond polymer fiber-rich region including an inner surface and an outersurface; and (c) at least one third polymer boundary region containing aportion of the first polymer fiber-free region and a portion of thesecond polymer fiber-rich region. Whereas, the outer surface of thefirst polymer fiber-free region is integrally bonded to the innersurface of the second polymer fiber-rich region forming the at least onethird polymer boundary region disposed between the first polymerfiber-free region and the second polymer fiber-rich region; wherein thethird polymer boundary region further comprises a contiguous boundary ofa non-delineated width between the first polymer fiber-free region andthe second polymer fiber-rich region; and wherein the first polymerfiber-free region is integrally attached to the second polymerfiber-rich region such that the first polymer fiber-free region andsecond polymer fiber-rich region are infused together forming the atleast one third polymer boundary region.

An apparatus for manufacturing a fiber-reinforced composite articleuseful for contaminant removal comprising: (I) a means for disposing agel material layer onto the surface of a mandrel; (II) a means forintroducing a fiber reinforcement into a resin impregnation means; (III)a resin impregnation means for impregnating the fiber reinforcement of(II) with a polymer resin to form a polymer fiber-reinforced layermaterial; (IV) a means for disposing the resin impregnatedfiber-reinforced layer material of (III) onto the surface of the gelmaterial layer of (I); and (V) a means for curing the combination of thegel material layer and the resin impregnated fiber-reinforced layermaterial to form at least one single layer of a fiber-reinforcedcomposite including the following regions in said at least one singlelayer: (a) at least one first polymer fiber-free region containingmaterial adapted for removing contaminants, said contaminant removalmaterial integrated into the first polymer fiber-free region; said firstpolymer fiber-free region including an inner surface and an outersurface; (b) at least one second polymer fiber-rich region containingfiber reinforcement material; said second polymer fiber-rich regionincluding an inner surface and an outer surface; and (c) at least onethird polymer boundary region containing a portion of the first polymerfiber-free region and a portion of the second polymer fiber-rich region.Whereas, the outer surface of the first polymer fiber-free region isintegrally bonded to the inner surface of the second polymer fiber-richregion forming the at least one third polymer boundary region disposedbetween the first polymer fiber-free region and the second polymerfiber-rich region; wherein the third polymer boundary region furthercomprises a contiguous boundary of a non-delineated width between thefirst polymer fiber-free region and the second polymer fiber-richregion; and wherein the first polymer fiber-free region is integrallyattached to the second polymer fiber-rich region such that the firstpolymer fiber-free region and second polymer fiber-rich region areinfused together forming the at least one third polymer boundary region.

A process for manufacturing a fiber-reinforced composite article usefulfor contaminant removal comprising the steps of: (A) disposing a gelmaterial layer onto the surface of a mandrel; (B) introducing a fiberreinforcement into a polymer resin impregnation means; (C) impregnatingthe fiber reinforcement of step (B) with a polymer resin to form apolymer fiber-reinforced layer material; (D) disposing the resinimpregnated fiber-reinforced layer material of step (C) onto the surfaceof the gel material layer of (I); and (E) bonding polymer gel materiallayer to the polymer fiber-reinforced layer material by curing thecombination of the gel material layer and the resin impregnatedfiber-reinforced layer material to form at least one single layer of afiber-reinforced composite including the following regions in said atleast one single layer: (a) at least one first polymer fiber-free regioncontaining material adapted for removing contaminants, said contaminantremoval material integrated into the first polymer fiber-free region;said first polymer fiber-free region including an inner surface and anouter surface; (b) at least one second polymer fiber-rich regioncontaining fiber reinforcement material; said second polymer fiber-richregion including an inner surface and an outer surface; and (c) at leastone third polymer boundary region containing a portion of the firstpolymer fiber-free region and a portion of the second polymer fiber-richregion. Whereas, the outer surface of the first polymer fiber-freeregion is integrally bonded to the inner surface of the second polymerfiber-rich region forming the at least one third polymer boundary regiondisposed between the first polymer fiber-free region and the secondpolymer fiber-rich region; wherein the third polymer boundary regionfurther comprises a contiguous boundary of a non-delineated widthbetween the first polymer fiber-free region and the second polymerfiber-rich region; and wherein the first polymer fiber-free region isintegrally attached to the second polymer fiber-rich region such thatthe first polymer fiber-free region and second polymer fiber-rich regionare infused together forming the at least one third polymer boundaryregion. The process may further provide for the exposed surface area ofthe material adapted for removing contaminants is increased by thefurther steps of: (v) applying a pre-processing treatment to the surfaceupon which the composite article is formed; and (vi) applying apost-processing treatment to the composite article. The post-processingtreatment may be a mechanical, thermal, electrical or chemicalpost-processing method.

A process for removing contaminants from a liquid fluid in contact witha fiber-reinforced composite article comprising the steps of: (a)providing a fiber-reinforced composite article useful for contaminantremoval comprising at least one single layer of a fiber-reinforcedcomposite including the following regions in said at least one singlelayer: (a) at least one first polymer fiber-free region containingmaterial adapted for removing contaminants, said contaminant removalmaterial integrated into the first polymer fiber-free region; said firstpolymer fiber-free region including an inner surface and an outersurface; (b) at least one second polymer fiber-rich region containingfiber reinforcement material; said second polymer fiber-rich regionincluding an inner surface and an outer surface; and (c) at least onethird polymer boundary region containing a portion of the first polymerfiber-free region and a portion of the second polymer fiber-rich region.Whereas, the outer surface of the first polymer fiber-free region isintegrally bonded to the inner surface of the second polymer fiber-richregion forming the at least one third polymer boundary region disposedbetween the first polymer fiber-free region and the second polymerfiber-rich region; wherein the third polymer boundary region furthercomprises a contiguous boundary of a non-delineated width between thefirst polymer fiber-free region and the second polymer fiber-richregion; and wherein the first polymer fiber-free region is integrallyattached to the second polymer fiber-rich region such that the firstpolymer fiber-free region and second polymer fiber-rich region areinfused together forming the at least one third polymer boundary region.Further comprising, (β) contacting a liquid fluid with the first polymerfiber-free region containing material adapted for removing contaminantssuch the material adapted for removing contaminants in the first polymerfiber-free region adsorbs one or more contaminants from the liquidfluid.

EXAMPLES

The following examples and comparative examples further illustrate thepresent invention in more detail but are not to be construed to limitthe scope thereof.

In the following Examples, various materials, terms and designations areused and are explained as follows:

EEW stands for epoxide equivalent weight.

AHEW stands for amine hydrogen equivalent weight.

D.E.R. 383 is an epoxy resin having an EEW of 171 and commerciallyavailable from The Dow Chemical Company.

D.E.N. 438 is an epoxy resin having an EEW of 179 and commerciallyavailable from The Dow Chemical Company.

VORAFORCE™ TW 120 is a formulated amine hardener having an AHEW of 36and commercially available from The Dow Chemical Company.

BYK 940 is a dispersion-aiding additive and commercially available fromAltana.

BaSO₄ powder was obtained from Excalibar Minerals.

Standard measurements, analytical equipment and methods were used in theExamples as follows:

EEW Measurements

The EEW of the resin was measured according to the procedure describedin ASTM D-1652 (2011).

AHEW Measurements

The AHEW of the resin was calculated after finding the amine valueaccording to the procedure described in ISO 9702 (1996).

Viscosity Measurements

The viscosity of the resin was measured according to the proceduredescribed in ASTM D-445(2015) at 25° C.

General Procedure of Filament Winding Process

A composite pipe of the present invention can be manufactured using afilament winding process. Filament winding is one of the more importantcomposite production methods in terms of number of users and totalnumber of fabricated parts. The filament winding process begins withfiber tows coming from spools of glass or carbon fibers mounted on acreel. The fibers are gathered together and collected through a type offiber guide (i.e., a “comb”) to form a band. The number of the fibersbrought together determines the band width. The band is pulled through aresin bath (containing a resin and a hardener mixed together such thatthe formulation is active). The resin from the resin bath impregnatesthe pulled fiber tow. The fibers are then drawn through a roller orwiper system to achieve the desired resin content on the fibers; andthen the fibers are drawn through a payoff. The “payoff” is the point atwhich the fiber contacts a moving carriage and directs the fibers on toa rotating mandrel. This method of production is efficient for producingany type of cylindrical part. Furthermore, as the complexity andcapability of filament winding machines increases other non-cylindricalparts can also be wound using a filament winding method.

General Procedure of Hand-Lay Up

A composite article of the present invention, alternatively, can bemanufactured through a hand lay-up method utilizing two differentproduction steps. Hand lay-up is the simplest and oldest open moldingmethod of the composite fabrication processes. It is a low volume, laborintensive method suited especially for large components. Glass, carbonor other reinforcing mat or woven fabric or roving is positionedmanually in the open mold, and resin is poured, brushed, or sprayed overand into the glass plies. Entrapped air is removed manually withsqueegees or rollers to complete the laminates structure. Curing isinitiated by a catalyst in the resin formulation, which hardens thefiber reinforced resin composite without external heat. Post cure toachieve higher mechanical properties is often required.

Example 1—Manufacture of Composite Article Via Filament Winding

Two different formulated compositions were used to produce a singlecomposite article using a filament winding process. The two compositionsare described in Table I. The two formulations or compositions weredesigned for advantageously having a fiber-free (i.e., resin-rich) layercontaining barium sulfate particles near the surface of the compositearticle (“first composition”) and a fiber-rich (“second composition”)layer chemically bonded to the resin-rich layer providing mechanicalreinforcement.

The first composition (“Gel Layer” in Table I), was applied as a gellayer to a rotating mandrel and was designed to have high initialviscosity (e.g., >20,000 mPa-s) to prevent sagging and dripping duringapplication of gel layer onto the mandrel; and a fast gel time (e.g., <1hour at 25° C.) to advantageously allow the gel layer to be processedmore readily.

The second composition (“Fiber-Reinforced Layer” in Table I) wasdesigned as a low viscosity formulation (e.g., ˜500 mPa-s) for atraditional open-bath filament winding manufacturing process. The lowviscosity of the second composition ensures thorough and homogenousfiber wet out during the composite article manufacture. The secondcomposition has a longer gel time (e.g., >6 hours at 25° C.) than thefirst composition; and has desirable toughness properties upon curing(e.g., K_(1C) Mode Fracture Toughness ˜0.75 MPa-m^(1/2)).

TABLE I Formulations for Gel layer and Fiber-Reinforced Layer for Use ina Filament Winding System Gel Layer Fiber-Reinforced Component (wt %)Layer (wt %) D.E.R. 383 0.0 71.6 D.E.N. 438 20.8 0.0 1,4 butanedioldiglycidyl ether 0.0 11.7 VORAFORCE ™ TW 120 4.2 16.7 BaSO₄ powder 75.00.0 Total 100 100

Example 2—Manufacture of Composite Article Via Hand Lay-Up

In this Example 2, two different polymer compositions are used toproduce a composite article using a hand lay-up process. The two polymercompositions are described in Table II. The two formulations orcompositions are designed for advantageously having a fiber-free (i.e.,resin-rich) layer containing barium sulfate particles near the surfaceof the composite article (“first composition”) and a fiber-rich (“secondcomposition”) layer chemically bonded to the resin-rich layer providingmechanical reinforcement.

The first polymer composition (“Gel Layer” in Table II), is applied as agel layer to a substrate and is designed to have high initial viscosity(e.g., >20,000 mPa-s) to prevent sagging and dripping during applicationof gel layer; and a fast gel time (e.g.,

<1 hour at 25° C.) to advantageously allow the gel layer to be processedmore readily.

The second polymer composition (“Fiber-Reinforced Layer” in Table II) isa commercially available conventional formulation have a low viscosityfor homogenous fiber bundle impregnation; and exhibiting a long gel time(e.g., >6 hours at 25° C.).

TABLE II Formulations for Gel layer and Fiber-Reinforced Layer for Usein a Hand Lay-Up System Gel-Layer Fiber-Reinforced Component (wt %)Layer (wt %) D.E.R. 383 0.0 69.5 D.E.N. 438 29.8 0.0 1,4 butanedioldiglycidyl ether 0.0 5.2 methyl-p-toluene sulfonate 0.1 0.2polyetherdiamine, 230 MW 10.1 25.1 BaSO₄ powder 60.0 0.0 Total 100 100

Examples 3-5—Absorption of Radium-226

Three trials were run to quantify the amount of radionuclide removalusing a fiber-reinforced composite of the present invention as follows:

General Procedure of Testing

In general, the experiments related to the absorption of Radium-226(Ra-226) were carried out using two granular materials containingdifferent mass fractions of barium sulfate (GM1 and GM2). The threetrials were: (1) both materials were tested at 50 degrees Celsius (°C.), 70° C. and 90° C., (2) material GM1 in brine and in a modifiedbrine lacking barium sulfate are tested at 90° C., and (3) bariumsulfate in brine and in a modified brine lacking barium sulfate aretested at 90° C.

The general procedure included contacting the two materials with brinecontaining Ra-226 at three temperatures. The brine contained chloridesof calcium, sodium and barium. Samples of brine were taken at varioustimes and analyzed to assess the amount of Ra-226 remaining in thebrine. The amount of Ra-226 absorbed by the materials was assessed atthe end of the experiment.

Samples of material and brine were placed in 500 ml glass bottles andheld at a fixed temperature. A water bath was used for the 50° C. trialand electric ovens were used for the 70° C. and the 90° C. trials. Themixture was mixed by swirling several times during each experiment.

A standard solution of Ra-226, commercially available from IsotopeProducts Laboratories, was diluted with dilute nitric acid to obtain aworking solution. Portions of the working solution were then dispensedfor each of the trials by pipetting.

One-liter lots of brine are prepared by weighing. The brine contains 5.0wt %, 2.6 wt %, and 0.07 wt % of NaCl, CaCl₂ and BaCl₂.2H₂O,respectively. The pH of the brine was adjusted to between 7.5 and 8.0using solutions of sodium hydroxide and hydrochloric acid.

A portion of brine was weighed out for each test. A solution (2.457milliliters (mL)) containing approximately 5,000 picoCuries of Ra-226was added to the brine, and the pH of the brine was readjusted. One ofthe brine portions was added to a

pre-weighed sample of material to start each test.

The detection of Ra-226 in brine samples was determined by LiquidScintillation Counting (LSC). After the Ra-226 exposure to the fibercomposite was complete, the detection of Ra-226 captured in thecontaminant-capturing particles of the material was determined byGamma-ray Spectrometry.

Before LSC, each aliquot was gently evaporated in order to expel Rn-222,which interfered with the Ra-226 measurement. Two counting windows wereused: one registered counts due to both Ra-226 and Rn-222 and the otherregistered counts only due to Rn-222. A correction factor wasestablished using water from a Radon generator and was used to correctfor Rn-222 interference on Ra-226.

Example 3—Trial 1

45 g of material and 180 g of brine are used for each test. At eachsampling, the bottles are weighed and aliquots are withdrawn from openedbottles using an air displacement pipette. After the final sampling, thematerial is removed from the exposure bottle by slurrying with deionizedwater and was then briefly rinsed with further deionized water beforepackaging for gamma-ray spectrometry. Results were corrected for theeffects of pipetting hot liquids and for losses due to evaporation. Fourcontrol preparations were tested to assess any contribution from thematerials used. The results of the first trial are described in TablesIII and IV.

TABLE III Results by Liquid Scintillation Counting Temper- Fractionature Remain- Uncer- Medium (° C.) Time ing^((a)) tainty^((b)) GM1 50 1hour 0.99 0.03 4 hours 0.98 0.03 3 days 0.89 0.03 7 days 0.89 0.03 GM250 1 hour 1.00 0.03 4 hours 0.89 0.03 3 days 0.86 0.03 7 days 0.89 0.03GM1 70 1 hour 0.99 0.03 4 hours 0.96 0.03 3 days 0.95 0.03 7 days 1.020.03 GM2 70 1 hour 0.96 0.03 4 hours 0.93 0.03 3 days 0.91 0.03 7 days0.86 0.03 GM1 90 1 hour 1.04 0.03 4 hours 1.06 0.03 3 days 0.88 0.03 7days 0.80 0.02 GM2 90 1 hour 1.02 0.03 4 hours 1.05 0.03 3 days 0.990.03 7 days 1.03 0.03 Notes for Table III: ^((a))count rate divided bythe count rate for a sample taken at the start of the experiment ^((b))1standard deviation, computed from counting statistics

The results were corrected for interference due to Radon, losses due toevaporation and the effect of hot solutions on the operation ofpipettes. Uncertainty arising from pipetting could not be assessed andwas not included in the estimates given above.

TABLE IV Gamma-ray Spectrometry. Temper- Ra-226 % of Original atureActivity 1 Standard Ra-226 1 Standard Medium (° C.) (Bq) DeviationActivity Deviation GM1 70 10.3 0.5 5.6 0.3 GM2 70 19.8 0.6 10.7 0.3 GM190 12.8 0.4 6.9 0.2

Example 4—Trial 2

90 g of material GM1 and 360 g of brine were used for each test. One lotof brine contained barium, the other did not. In both cases, the pH wasadjusted to 7.5 to 8.0. The contact was carried out at 90° C. Eachportion of material was rinsed three times with deionized water toremove fines before addition of brine. Slight cloudiness was observed inthe final rinse.

At each sampling, the bottles were weighed and aliquots were withdrawnfrom bottles using a syringe and a thin tube that passed through a smallhole in the bottle cap; and placed in pre-weighed vials. The amountcollected was determined by re-weighing the vials, and was included incalculations.

The brine was sampled before mixing with material, immediately aftermixing, at 3 days and at 7 days. Duplicate aliquots were taken at 3 daysand 7 days. After the final sampling, the brine was thoroughly drainedfrom the material and the material was then packaged for gamma-rayspectrometry. The results of the second trial are described in Tables Vand VI.

TABLE V Liquid Scintillation Counting Temper- Fraction ature Remain-Uncer- Material Brine (° C.) Time ing^((a)) tainty^((b)) GM1 With Ba 90before 1.00 mixing after 0.93 0.02 mixing 7 days 0.78, 0.79 0.02 GM1Without Ba 90 before 1.00 mixing after 0.86 0.01 mixing 3 days 0.49,0.50 0.01 7 days 0.51, 0.51 0.01 Notes for Table V: ^((a))count ratedivided by the count rate for a sample taken before the start of theexperiment ^((b))1 standard deviation, computed from counting statistics

TABLE VI Gamma-ray Spectrometry Ra-226 % of Original Activity 1 StandardRa-226 1 Standard Medium Brine (Bq) Deviation Activity Deviation GM1With Ba 42.5 1.3 26.1 0.9 GM1 Without Ba 98.9 1.7 56.6 1.3

Example 5—Trial 3

0.72 g of barium sulfate and 360 g of brine were used for each test. Onelot of brine contained barium, the other did not. In both cases, the pHwas adjusted to 7.5 to 8.0. The contact was carried out at 90° C.

At each sampling, the bottles were weighed and aliquots were withdrawnfrom bottles using a syringe and a thin tube that passed through a smallhole in the bottle cap, and placed in pre-weighed vials. The amountcollected was determined by re-weighing the vials, and was included incalculations.

The brine was sampled before mixing with barium sulphate, immediatelyafter mixing at 3 days. Duplicate aliquots were taken at 3 days. As thebarium sulphate was initially too finely divided to settle, the initialportion was filtered. By 3 days, filtering was unnecessary.

After the final sampling, the barium sulfate was collected by filtering,using filtrate to collect as much of the still very finely divided solidas possible. There may have been small losses to the walls of thebottle. The filters were then packaged for gamma-ray spectrometry. Theresults of the third trial are described in Tables VII and VIII.

TABLE VII Liquid Scintillation Counting Temper- Fraction ature Remain-Uncer- Material Brine (° C.) Time ing^((a)) tainty^((b)) BaSO₄ With Ba90 before 1.00 mixing after 0.96 0.02 mixing 3 days 0.73, 0.69 0.02BaSO₄ Without Ba 90 before 1.00 mixing after 0.46 0.02 mixing 3 days0.047, 0.047 0.009 Notes for Table VII: ^((a))count rate divided by thecount rate for a sample taken before the start of the experiment ^((b))1standard deviation, computed from counting statistics

TABLE VIII Gamma-ray Spectrometry Ra-226 % of Original Activity 1Standard Ra-226 1 Standard Medium Brine (Bq) Deviation ActivityDeviation BaSO₄ With Ba 44.8 0.6 31.5 0.7 BaSO₄ Without Ba 122 2 85 2

What is claimed is:
 1. A fiber-reinforced composite article useful forcontaminant removal comprising at least one single layer of afiber-reinforced composite including the following regions in said atleast one single layer: (a) at least one first polymer fiber-free regioncontaining material adapted for removing contaminants, said contaminantremoval material integrated into the first polymer fiber-free region;said first polymer fiber-free region including an inner surface and anouter surface; (b) at least one second polymer fiber-rich regioncontaining fiber reinforcement material; said second polymer fiber-richregion including an inner surface and an outer surface; and (c) at leastone third polymer boundary region containing a portion of the firstpolymer fiber-free region and a portion of the second polymer fiber-richregion; wherein the outer surface of the first polymer fiber-free regionis integrally bonded to the inner surface of the second polymerfiber-rich region forming the at least one third polymer boundary regiondisposed between the first polymer fiber-free region and the secondpolymer fiber-rich region; wherein the third polymer boundary regionfurther comprises a contiguous boundary of a non-delineated widthbetween the first polymer fiber-free region and the second polymerfiber-rich region; and wherein the first polymer fiber-free region isintegrally attached to the second polymer fiber-rich region such thatthe first polymer fiber-free region and second polymer fiber-rich regionare infused together forming the at least one third polymer boundaryregion.
 2. The composite of claim 1, wherein there fiber reinforcedregion contains fiber reinforcement is glass, carbon, aramid, andmixtures thereof.
 3. The composite of claim 1, wherein the fiber in thefiber-reinforced region is continuous reinforcing fibers ordiscontinuous reinforcing fibers.
 4. The composite of claim 1, whereinthe fiber orientation in the fiber-reinforced region is any orientationin a three-dimensional coordinate frame.
 5. The composite of claim 1,wherein the polymer of the fiber-free region is a thermosetting resin, athermoplastic resin, or a combination thereof.
 6. The composite of claim1, wherein the polymer of the fiber-reinforced region is a thermosettingresin, a thermoplastic resin, or a combination thereof.
 7. The compositeof claim 1, wherein the fiber-reinforced composite includesmulti-functional materials, in addition to the contaminant removalmaterials, for increasing the mechanical, chemical, thermal andelectrical properties of the fiber-reinforced composite.
 8. Thecomposite of claim 1, wherein the composite includes a plurality offiber-free regions.
 9. The composite of claim 1, wherein the compositeincludes a plurality of fiber-reinforced regions.
 10. The composite ofclaim 1, wherein the composite includes a plurality of fiber-freeregions and fiber-reinforced regions in any layered order in thecomposite.
 11. The composite of claim 1, wherein the material adaptedfor removing contaminants is BaSO₄, MnO₂ or any combination thereof. 12.The composite of claim 1 comprising a conduit, pipe, or piping.
 13. Aprocess for manufacturing a fiber-reinforced composite article usefulfor contaminant removal at least one single layer of a fiber-reinforcedcomposite comprising the steps of: (i) providing a formulation forforming at least one first polymer fiber-free gel layer; (ii) applyingthe first polymer fiber-free gel layer formulation of (i) onto a mandrelof a filament winding process such that the polymer fiber-free gel layerformulation forms a polymer fiber-free gel layer of a predeterminedthickness on the mandrel; (iii) providing a formulation for forming atleast one second polymer fiber-rich layer; (iv) applying the secondpolymer fiber-rich layer formulation of (iii) onto the surface of thepolymer fiber-free gel layer produced in step (ii) such that the secondpolymer fiber-rich layer formulation forms a second polymer fiber-richlayer of a predetermined thickness disposed on the first polymerfiber-free gel layer which is disposed on the mandrel; and (v) curingthe first polymer fiber-free gel layer and second polymer fiber-richlayer to form at least one single layer of a fiber-reinforced composite;wherein the at least one single layer of a fiber-reinforced compositeincludes the following regions in said single layer: (a) at least onefirst polymer fiber-free region containing material adapted for removingcontaminants, said contaminant removal material integrated into thefirst polymer fiber-free region; said first polymer fiber-free regionincluding an inner surface and an outer surface; (b) at least one secondpolymer fiber-rich region containing fiber reinforcement material; saidsecond polymer fiber-rich region including an inner surface and an outersurface; and (c) at least one third polymer boundary region containing aportion of the first polymer fiber-free region and a portion of thesecond polymer fiber-rich region; wherein the outer surface of the firstpolymer fiber-free region is integrally bonded to the inner surface ofthe second polymer fiber-rich region forming the at least one thirdpolymer boundary region disposed between the first polymer fiber-freeregion and the second polymer fiber-rich region; wherein the thirdpolymer boundary region further comprises a contiguous boundary of anon-delineated width between the first polymer fiber-free region and thesecond polymer fiber-rich region; and wherein the first polymerfiber-free region is integrally attached to the second polymerfiber-rich region such that the first polymer fiber-free region andsecond polymer fiber-rich region are infused together forming the atleast one third polymer boundary region.
 14. The process of claim 13,wherein the fiber-free region is applied to the fiber-reinforced regionby a manual lay-up method or an automated lay-up method.
 15. The processof claim 13, wherein the fiber-reinforced composite is produced by acomposite fabrication method including injection molding, compressionmolding, pultrusion, and filament winding.